Beta-cyclodextrin (β-CD) was successfully loaded on the surface of glass beads without spacer group or cross-linking agent. The directly loaded β-CD was stable in toluene and methanol flows but critically hurt in more polar solvent such as water and dimethylformamide. Cross-linking could stabilize the directly bonded β-CD glass beads. Pore openings of cyclodextrin can be narrowed or blocked by end-capping agent, spacer groups, and cross-linking agents. The β-CD directly bonded glass beads have a capability to form inclusion complexes with larger host molecules because this method can avoid pore narrowing and blocking problems.